The present invention relates to a stabilizer mixture containing two different sterically hindered amine compounds and at least one Mg- and/or Zn-compound, the use of this mixture for stabilizing an organic material, in particular a polyolefin, against degradation induced by light, heat or oxidation and the organic material thus stabilized. The stabilization of polyolefins is described in numerous publications, for example in U.S. Pat. Nos. 4,929,652, 5,025,051, 5,037,870, EP-A-276,923, EP-A-290,388, EP-A-429,731, EP-A-468,923, EP-A-661,341, EP-A-690,094, DE-A-19,545,896 (Derwent 96-278,994/29; Chemical Abstracts 125:116779q), WO-A-95/25,767, GB-A-2,293,827, Chemical Abstracts 106:197407z, GB-A-2,332,678, WO-A-00/11,065, GB-A-2,316,409, GB-A-2, 332,677, Chemical Abstracts 132: 335,575t and Research Disclosure 34,549.
In more detail, the present invention relates to
a stabilizer mixture containing
(I) two different sterically hindered amine compounds, and
(II) at least one compound selected from the group consisting of an organic salt of Zn, an inorganic salt of Zn, Zn oxide, Zn hydroxide, an organic salt of Mg, an inorganic salt of Mg, Mg oxide and Mg hydroxide;
with the proviso that component (I) is different from the combination of the compounds (B-8-a) and (B-8-b): 
wherein n2 and n2* are a number from 2 to 50; and
with the proviso that, when
component (I) is the combination of the compounds (B-1-a-1) and (B-7-a): 
wherein b1 is a number from 2 to 50, 
wherein n1 is a number from 2 to 50; and,
at the same time, component (II) is a Zn carboxylate;
the stabilizer mixture additionally contains as a further component
(X-1) a pigment or
(X-2) an UV absorber or
(X-3) a pigment and an UV absorber.
A preferred embodiment of the present invention relates to a stabilizer mixture containing as component (I) two different sterically hindered amine compounds wherein one sterically hindered amine compound is a compound of the formula (B-1-b) or (B-1-d): 
wherein b1 is a number from 2 to 20 and R6 is hydrogen, C1-C8alkyl, Oxe2x88x92, xe2x80x94OH, xe2x80x94CH2CN, C1-C18alkoxy, C5-C12cycloalkoxy, C3-C6alkenyl, C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl; or C1-C8acyl; and
the other sterically hindered amine compound is a compound of the formula (B-7-a) 
wherein n1 is a number from 2 to 20; and
component (II) is an organic salt of Zn, an inorganic salt of Zn, Zn oxide or Zn hydroxide; preferably Zn carboxylate.
Preferably, a stabilizer mixture containing a compound of the class (xcex2-1) as defined below, a compound of the class (xcex2-7) as defined below and Zn-carboxylate, in particular an organic salt of Zn, is disclaimed.
According to a preferred embodiment of the present invention, component (II) is an organic salt of Mg, an inorganic salt of Mg, Mg oxide or Mg hydroxide, when component (I) is the combination of a compound of the class (xcex2-1) as defined below, and a compound of the class (xcex2-7) as defined below.
The stabilizer mixtures according to the present invention preferably do not contain a mineral oil.
The two different sterically hindered amine compounds of component (I) are preferably selected from the group consisting of the following classes
(xcex1-1) a compound of the formula (A-1): 
in which
E1 is hydrogen, C1-C8alkyl, Oxe2x88x92, xe2x80x94OH, xe2x80x94CH2CN, C1-C18alkoxy, C5-C12cycloalkoxy, C3-C6alkenyl, C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl; or
C1-C8acyl,
m1 is 1, 2 or 4,
if m1 is 1, E2 is C1-C25alkyl,
if m1 is 2, E2 is C1C14alkylene or a group of the formula (a-I): 
wherein E3 is C1-C10alkyl or C2-C10alkenyl, E4 is C1-C10alkylene, and
E5 and E6 independently of one another are C1-C4alkyl, cyclohexyl or methylcyclohexyl, and
if m1 is 4, E2 is C4-C10alkanetetrayl;
(xcex1-2) a compound of the formula (A-2): 
in which
two of the radicals E7 are xe2x80x94COOxe2x80x94(C1-C20alkyl), and
two of the radicals E7 are a group of the formula (a-II): 
with E8 having one of the meanings of E1;
(xcex1-3) a compound of the formula (A-3): 
in which
E9 and E10 together form C2-C14alkylene,
E11 is hydrogen or a group xe2x80x94Z1xe2x80x94COOxe2x80x94Z2,
Z1 is C2-C14alkylene, and
Z2 is C1-C24alkyl, and
E12 has one of the meanings of E1;
(xcex1-4) a compound of the formula (A-4): 
wherein
the radicals E13 independently of one another have one of the meanings of E1,
the radicals E14 independently of one another are hydrogen or C1-C12alkyl, and
E15 is C1-C10alkylene or C3-C10alkylidene;
(xcex1-5) a compound of the formula (A-5): 
wherein
the radicals E16 independently of one another have one of the meanings of E1;
(xcex1-6) a compound of the formula (A-6): 
in which
E17 is C1-C24alkyl, and
E18 has one of the meanings of E1;
(xcex1-7) a compound of the formula (A-7): 
in which
E19, E20 and E21 independently of one another are a group of the formula (a-IlI): 
wherein E22 has one of the meanings of E1;
(xcex1-8) a compound of the formula (A-8): 
wherein
the radicals E23 independently of one another have one of the meanings of E1,
and E24 is hydrogen, C1-C12alkyl or C1-C12alkoxy;
(xcex1-9) a compound of the formula (A-9): 
wherein
m2 is 1, 2 or 3,
E25 has one of the meanings of E1, and
when m2 is 1, E26 is a group 
when m2 is 2, E26 is C2-C22alkylene, and
when m2 is 3, E26 is a group of the formula (a-IV): 
wherein the radicals E27 independently of one another are C2-C12alkylene, and
the radicals E28 independently of one another are C1-C12alkyl or C5-C12cycloalkyl;
(xcex1-10) a compound of the formula (A-10): 
wherein
the radicals E29 independently of one another have one of the meanings of E1, and
E30 is C2-C22alkylene, C5-C7cycloalkylene, C1-C4alkylenedi(C5-C7cycloalkylene), phenylene or phenylenedi(C1-C4alkylene);
(xcex2-1) a compound of the formula (B-1): 
in which
R1, R3, R4 and R5 independently of one another are hydrogen, C1-C12alkyl, C5-C12cycloalkyl, C1-C4-alkyl-substituted C5-C12cycloalkyl, phenyl, phenyl which is substituted by xe2x80x94OH and/or C1-C10alkyl; C7-C9phenylalkyl, C7-C9phenylalkyl which is substituted on the phenyl radical by xe2x80x94OH and/or C1-C10alkyl; or a group of the formula (b-I): 
R2 is C2-C18alkylene, C5-C7cycloalkylene or C1-C4alkylenedi(B5xe2x80x94C7cycloalkylene), or
the radicals R1, R2 and R3, together with the nitrogen atoms to which they are bonded, perform a 5- to 10-membered heterocyclic ring, or
R4 and R5, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring,
R6 is hydrogen, C1-C8alkyl, Oxe2x88x92, xe2x80x94OH, xe2x80x94CH2CN, C1-C18alkoxy, C5-C12cycloalkoxy, C3-C6alkenyl,
C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl; or
C1-C8acyl, and
b1 is a number from 2 to 50,
with the proviso that at least one of the radicals R1, R3, R4 and R5 is a group of the formula (b-I);
(xcex2-2) a compound of the formula (B-2): 
wherein
R7 and R11 independently of one another are hydrogen or C1-C12alkyl,
R8, R9 and R10 independently of one another are C2-C10alkylene, and
X1, X2, X3, X4, X5, X6, X7 and X8 independently of one another are a group of the formula (b-II): 
in which R12 is hydrogen, C1-C12alkyl, C5-C12cycloalkyl, C1-C4alkyl-substituted C5-C12cycloalkyl, phenyl, xe2x80x94OHxe2x80x94 and/or C1-C10alkyl-substituted phenyl, C7-C9phenylalkyl, C7-C9phenylalkyl which is substituted on the phenyl radical by xe2x80x94OH and/or C1-C10alkyl; or a group of the formula (b-I) as defined above, and
R13 has one of the meanings of R6;
(xcex2-3) a compound of the formula (B-3): 
in which
R14 is C1-C10alkyl, C5-C12cycloalkyl, C1-C4alkyl-substituted C5-C12cycloalkyl, phenyl or
C1-C10alkyl-substituted phenyl,
R15 is C3-C10alkylene,
R16 has one of the meanings of R6, and
b2 is a number from 2 to 50;
(xcex2-4) a compound of the formula (B-4): 
in which
R17 and R21 independently of one another are a direct bond or a xe2x80x94N(X9)xe2x80x94COxe2x80x94X10xe2x80x94COxe2x80x94N(X11)-group, where X9 and X11 independently of one another are hydrogen, C1-C8alkyl, C5-C12cycloalkyl, phenyl, C7-C9phenylalkyl or a group of the formula (b-I),
X10 is a direct bond or C1-C4alkylene,
R18 has one of the meanings of R6,
R19, R20, R23 and R24 independently of one another are hydrogen, C1-C30alkyl,
C5-C12cycloalkyl or phenyl,
R22 is hydrogen, C1-C30alkyl, C5-C12cycloalkyl, phenyl, C7-C9phenylalkyl or a group of the formula (b-I), and
b3 is a number from 1 to 50;
(xcex2-5) a compound of the formula (B-5): 
in which
R25, R26, R27, R28 and R29 independently of one another are a direct bond or C1-C10alkylene,
R30 has one of the meanings of R6, and
b4 is a number from 1 to 50;
(xcex2-6) a product (B-6) obtainable by reacting a product, obtained by reaction of a polyamine of the formula (B-6-1) with cyanuric chloride, with a compound of the formula (B-6-2):
H2Nxe2x80x94(CH2)b5xe2x80x2xe2x80x94NHxe2x80x94(CH2)b5xe2x80x3xe2x80x94NHxe2x80x94(CH2)b5xe2x80x2xe2x80x3xe2x80x94NH2xe2x80x83xe2x80x83(B-6-1)

in which
b5xe2x80x2, b5xe2x80x3 and b5xe2x80x2xe2x80x3 independently of one another are a number from 2 to 12,
R31 is hydrogen, C1-C12alkyl, C5-C12cycloalkyl, phenyl or C7-C9phenylalkyl, and
R32 has one of the meanings of R6;
(xcex2-7) a compound of the formula (B-7): 
wherein A1 is hydrogen or C1-C4alkyl,
A2 is a direct bond or C1-C10alkylene, and
n1 is a number from 2 to 50;
(xcex2-8) at least one compound of the formulae (B-8-a) and (B-8-b): 
wherein n2 and n2* are a number from 2 to 50;
(xcex2-9) a compound of the formula (B-9): 
wherein A3 and A4 independently of one another are hydrogen or C1-C8alkyl, or A3 and A4 together form a C2-C14alkylene group, and
the variables n3 independently of one another are a number from 1 to 50; and
(xcex2-10) a compound of the formula (B-10): 
wherein n4 is a number from 2 to 50,
A5 is hydrogen or C1-C4alkyl,
the radicals A6 and A7 independently of one another are C1-C4alkyl or a group of the formula (b-I),
with the proviso that at least 50% of the radicals A7 are a group of the formula (b-I).
Examples of component (I) are:
A compound selected from the class xcex1-1 and a compound selected from the class xcex1-3, xcex1-5, xcex1-6, xcex1-7, xcex1-9, xcex1-10, xcex2-1, xcex2-2, xcex2-3, xcex2-4, xcex2-5, xcex2-6, xcex2-7, xcex2-8 or xcex2-9.
A compound selected from the class xcex1-3 and a compound selected from the class xcex1-5, xcex1-6, xcex1-7, xcex1-9, xcex1-10, xcex2-1, xcex2-2, xcex2-3, xcex2-4, xcex2-5, xcex2-6, xcex2-7, xcex2-8 or xcex2-9.
A compound selected from the class xcex1-5 and a compound selected from the class xcex1-6, xcex1-7, xcex1-9, xcex1-10, xcex2-1, xcex2-2, xcex2-3, xcex2-4, xcex2-5, xcex2-6, xcex2-7, xcex2-8 or xcex2-9.
A compound selected from the class xcex1-6 and a compound selected from the class xcex1-9, xcex1-10, xcex2-1, xcex2-2, xcex2-3, xcex2-4, xcex2-5, xcex2-6, xcex2-7, xcex2-8 or xcex2-9.
A compound selected from the class xcex1-7 and a compound selected from the class xcex1-9, xcex1-10, xcex2-1, xcex2-2, xcex2-3, xcex2-4, xcex2-5, xcex2-6, xcex2-7, xcex2-8 or xcex2-9.
A compound selected from the class xcex1-10 and a compound selected from the class xcex2-1, xcex2-2, xcex2-3, xcex2-4xcex2-5, xcex2-6, xcex2-7, xcex2-8 or xcex2-9.
A compound selected from the class xcex2-1 and a compound selected from the class xcex2-2, xcex2-3, xcex2-4, xcex2-5, xcex2-6, xcex2-7, xcex2-8, xcex2-9 or xcex2-10.
A compound selected from the class xcex2-2 and a compound selected from the class xcex2-3, xcex2-4, xcex2-5, xcex2-6, xcex2-7, xcex2-8, xcex2-9 or xcex2-10.
A compound selected from the class xcex2-3 and a compound selected from the class xcex2-4, xcex2-5, xcex2-6, xcex2-7, xcex2-8, xcex2-9 or xcex2-10.
A compound selected from the class xcex2-4 and a compound selected from the class xcex2-5, xcex2-6, xcex2-7, xcex2-8, xcex2-9 or xcex2-10.
A compound selected from the class xcex2-5 and a compound selected from the class xcex2-6, xcex2-7, xcex2-8, xcex2-9 or xcex2-10.
A compound selected from the class xcex2-6 and a compound selected from the class xcex2-7, xcex2-8, xcex2-9 or xcex2-10.
A compound selected from the class xcex2-7 and a compound selected from the class xcex2-8, xcex2-9 or xcex2-10.
A compound selected from the class xcex2-8 and a compound selected from the class xcex2-9 or xcex2-10.
A compound selected from the class xcex2-9 and a compound selected from the class xcex2-10.
According to a preferred embodiment,
the two different sterically hindered amine compounds of component (I) are selected from the group consisting of the classes (xcex1-1), (xcex1-2), (xcex1-3), (xcex1-4), (xcex1-5), (xcex1-6), (xcex1-7), (xcex1-8), (xcex1-9) and (xcex1-10).
According to a further preferred embodiment,
the two different sterically hindered amine compounds of component (I) are selected from the group consisting of the classes (xcex2-1), (xcex2-2), (xcex2-3), (xcex2-4), (xcex2-5), (xcex2-6), (xcex2-7), (xcex2-8), (xcex2-9) and (xcex2-10).
According to another preferred embodiment,
one of the two different sterically hindered amine compounds of component (I) is selected from the group consisting of the classes (xcex1-1), (xcex1-2), (xcex1-3), (xcex1-4), (xcex1-5), (xcex1-6), (xcex2-7), (xcex2-8), (xcex1-9) and (xcex1-10), and
the other of the two different sterically hindered amine compounds of component (I) is selected from the group consisting of the classes (xcex2-1), (xcex2-2), (xcex2-3), (xcex2-4), (xcex2-5), (xcex2-6), (xcex2-7), (xcex2-8), (xcex2-9) and (xcex2-10).
One of the two different sterically hindered amine compounds of component (I) is preferably selected from the class (xcex2-1).
According to a particularly preferred embodiment,
one of the two different sterically hindered amine compounds of component (I) is selected from the class (xcex2-1), and
the other of the two different sterically hindered amine compounds of component (I) is selected from the class (xcex1-1) or (xcex2-7).
According to another particularly preferred embodiment,
one of the two different sterically hindered amine compounds of component (I) is selected from the class (xcex2-7), and
the other of the two different sterically hindered amine compounds of component (I) is selected from the class (xcex2-2).
The two different sterically hindered amine compounds of component (I) are preferably selected from different classes.
Examples of alkyl having up to 30 carbon atoms are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethyl-butyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, docosyl and triacontyl. One of the preferred definitions of E1, E8, E12, E13, E16, E18, E22, E23, E25, E29, R6, R13, R16, R18, R30 and R32 is C1-C4alkyl, especially methyl. R31 is preferably butyl.
Examples of alkoxy having up to 18 carbon atoms are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy. One of the preferred meanings of E1 is octoxy. E24 is preferably C1-C4alkoxy and one of the preferred meanings of R6 is propoxy.
Examples of C5-C12cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl. C5-C8Cycloalkyl, especially cyclohexyl, is preferred.
C1-C4Alkyl-substituted C5-C12cycloalkyl is for example methylcyclohexyl or dimethylcyclohexyl.
Examples of C5-C12cycloalkoxy are cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy. C5-C8Cycloalkoxy, in particular cyclopentoxy and cyclohexoxy, is preferred.
xe2x80x94OHxe2x80x94 and/or C1-C10alkyl-substituted phenyl is for example methylphenyl, dimethylphenyl, trimethylphenyl, tert-butylphenyl or 3,5-di-tert-butyl-4-hydroxyphenyl.
Examples of C7-C9phenylalkyl are benzyl and phenylethyl.
C7-C9Phenylalkyl which is substituted on the phenyl radical by xe2x80x94OH and/or by alkyl having up to 10 carbon atoms is for example methylbenzyl, dimethylbenzyl, trimethylbenzyl, tert-butylbenzyl or 3,5-di-tert-butyl-4-hydroxybenzyl.
Examples of alkenyl having up to 10 carbon atoms are allyl, 2-methallyl, butenyl, pentenyl and hexenyl. Allyl is preferred. The carbon atom in position 1 is preferably saturated.
Examples of acyl containing not more than 8 carbon atoms are formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, acryloyl, methacryloyl and benzoyl. C1-C8Alkanoyl, C3-C8alkenyl and benzoyl are preferred. Acetyl and acryloyl are especially preferred.
Examples of alkylene having up to 22 carbon atoms are methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene and decamethylene.
An example of C3-C10alkylidene is the group 
An example of C4-C10alkanetetrayl is 1,2,3,4-butanetetrayl.
An example of C5-C7cycloalkylene is cyclohexylene.
An example of C1-C4alkylenedi(C5-C7cycloalkylene) is methylenedicyclohexylene.
An example of phenylenedi(C1-C4alkylene) is methylene-phenylene-methylene or ethylene-phenylene-ethylene.
Where the radicals R1, R2 and R3, together with the nitrogen atoms to which they are attached, form a 5- to 10-membered heterocyclic ring, this ring is for example: 
A 6-membered heterocyclic ring is preferred.
Where the radicals R4 and R5, together with the nitrogen atom to which they are attached, form a 5- to 10-membered heterocyclic ring, this ring is for example 1-pyrrolidyl, piperidino, morpholino, 1-piperazinyl, 4-methyl-1-piperazinyl, 1-hexahydroazepinyl, 5,5,7-trimethyl-1-homopiperazinyl or 4,5,5,7-tetramethyl-1-homopiperazinyl. Morpholino is particularly preferred.
One of the preferred definitions of R19 and R23 is phenyl.
R26 is preferably a direct bond.
n1, n2, n2* and n4 are preferably a number from 2 to 25, in particular 2 to 20. n3 is preferably a number from 1 to 25, in particular 1 to 20.
b1 and b2 are preferably a number from 2 to 25, in particular 2 to 20.
b3 and b4 are preferably a number from 1 to 25, in particluar 1 to 20.
b5xe2x80x2 and b5xe2x80x2xe2x80x3 are preferably 3 and b5xe2x80x3 is preferably 2.
The compounds described above as components (I) and (II) are essentially known and commercially available. All of them can be prepared by known processes.
The preparation of the compounds of component (I) is disclosed, for example, in U.S. Pat. Nos. 5,679,733, 3,640,928, 4,198,334, 5,204,473, 4,619,958, 4,110,306, 4,110,334, 4,689,416, 4,408,051, SU-A-768,175 (Derwent 88-138,751/20), U.S. Pat. Nos. 5,049,604, 4,769,457, 4,356,307, 4,619,956, 5,182,390, GB-A-2,269,819, U.S. Pat. Nos. 4,292,240, 5,026,849, 5,071,981, 4,547,538, 4,976,889, 4,086,204, 6,046,304, 4,331,586, 4,108,829, 5,051,458, WO-A-94/12,544 (Derwent 94-177,274/22), DD-A-262,439 (Derwent 89-122,983/17), U.S. Pat. Nos. 4,857,595, 4,529,760, 4,477,615, CAS 136,504-96-6, U.S. Pat. Nos. 4,233,412, 4,340,534, WO-A-98/51,690 and EP-A-1,803.
The product (B-6) can be prepared analogously to known processes, for example by reacting a polyamine of formula (B-6-1) with cyanuric chloride in a molar ratio of from 1:2 to 1:4 in the presence of anhydrous lithium carbonate, sodium carbonate or potassium carbonate in an organic solvent such as 1,2-dichloroethane, toluene, xylene, benzene, dioxane or tert-amyl alcohol temperature of from xe2x88x9220xc2x0 C. to +10xc2x0 C., preferably from xe2x88x9210xc2x0 C. to +10xc2x0 C., in particular from 0xc2x0 C. to +10xc2x0 C., for from 2 to 8 hours, followed by reaction of the resultant product with a 2,2,6,6-tetramethyl-4-piperidylamine of the formula (B-6-2). The molar ratio of the 2,2,6,6-tetramethyl-4-piperidylamine to polyamine of the formula (B-6-1) employed is for example from 4:1 to 8:1. The quantity of the 2,2,6,6-tetramethyl-4-piperidylamine can be added in one portion or in more than one portion at intervals of a few hours.
The molar ratio of polyamine of the formula (B-6-1) to cyanuric chloride to 2,2,6,6-tetramethyl-4-piperidylamine of the formula (B-6-2) is preferebly from 1:3:5 to 1:3:6.